Laser Ablation ICP-MS Analyses Research Articles

Identifying xenocrystic tourmaline in Himalayan leucogranites

Abstract Tourmaline is a common autocrystic mineral in granitic and pegmatitic rocks that records valuable information on the physicochemical evolution of magmas. However, xenocrystic tourmaline that does not crystallize from host magmas is also common but seldom reported and notoriously difficult to identify. Here, autocrystic (Tur G) and xenocrystic (Tur P) tourmalines are identified in two-mica granites and granitic pegmatites from the Cuonadong leucogranites, eastern Himalaya. Electron backscatter diffraction (EBSD), coupled with electron-probe micro-analysis (EPMA) and laser ablation ICP-MS analyses (LA-ICP-MS), is used to discriminate xenocrystic from autocrystic tourmaline. Although both tourmalines have slightly different chemical compositions, the differences are insufficient to permit unambiguous discrimination. However, EBSD systematically shows complex intra-crystalline orientations and deformation xenocrystic grains, and undeformed crystal lattices are predominant in autocrystic grains. EBSD could be a useful tool to identify the origin of tourmaline in granitic rocks, particularly when geochemical analyses and/or geochronological measurements are inconclusive.

The nature and origin of pigments in black opal from Lightning Ridge, New South Wales, Australia

Black opal (opal-AG) owes its dark coloration to a fine-grained pigment commonly inferred to be mainly carbon, yet chemical compositions for black opals suggest there may be additional components. Here we search for such components in pigment concentrates prepared by dissolving black opal nodules (nobbies) from Lightning Ridge (NSW) in hydrofluoric acid, using electron microscopy (scanning electron microscopy, transmission electron microscopy), X-ray diffraction and laser-ablation ICP-MS. The results demonstrate the presence of sulfides—predominantly pyrite and chalcopyrite, with minor galena and Ti-oxide phases, as additional components of the pigment. ATR-FTIR analysis indicates the presence of C=O and C–H groups, consistent with an organic origin. Transmission electron microscopy images of pigment show variously deformed, originally spherical ∼100 nm particles rich in sulfide and carbon, which are interpreted as thin coatings of pigment on now dissolved opaline silica spheres. Laser-ablation ICP-MS analysis identifies remnant silica in pigment concentrates, which may be interpreted as opaline silica surviving HF treatment protected as inclusions in sulfides. When examined within the context of petrographic observations from more than 1000 opal nodules (nobbies) at Lightning Ridge, these new results suggest that pigment carbon and sulfides in the nodules formed microbially under initially anoxic groundwater conditions, within pre-existing cavities concurrently being filled with silica sol ultimately derived from chemical weathering of feldspar-rich volcaniclastic sediment. Intensely black pigment layers observed at the floor of many nodules indicate settling of dark, high-density (sulfide–Ti-oxide-rich) pigment within cavities, with the implication that sulfate-reducing bacterial (SRB) activity commences early during the silica sol-gel ripening process. Microbial activity may persist until after the cavity has completely filled with the silica sol, as illustrated by abundant black opals with uniformly distributed pigment. Pigment formed at this stage may no longer be able to settle out within the ripening and increasingly viscous silica gel, thus forming pigmentation throughout the opal cavity. The existence of ‘amber’, pigment-poor opal with intensely black basal pigment layers is interpreted as signalling a lack of sulfate to sustain further SRB activity, or a change to more oxidising conditions, possibly related to interaction with surface waters within a downward-penetrating weathering front. A change in redox conditions would shut off activity of SRB and thus sulfide pigment production and allow development of aerobic microbial activity as described by others.

Longitudinal and transverse variation of trace element concentrations in elephant and giraffe hair: implication for endogenous and exogenous contributions.

The spatial distribution of trace elements in hair is highly heterogeneous at the microscale. The relatively mild spatial variation of endogenous signal incorporated during hair growth may be amplified by orders of magnitude due to later exogenous contaminations. Here, we studied the longitudinal and transverse distributions of trace elements in elephant and giraffe hair and discussed the possible endogenous and exogenous contributions. Laser ablation ICP-MS analyses were performed on cross sections of hair to assess the surface contamination and transverse variation. We also removed the contaminated surface layer at various distances from hair root of single hair strands using physical abrasion and measured the concentrations by microwave digestion followed by ICP-MS. By comparing the concentrations of 11 trace elements between the intact and abraded hair segments as a function of distance from root and their laser ablation profiles, we rationalized the endogenous and exogenous contributions: Al and Ti concentrations are dominated by the exogenous contamination on the elephant hair surface, probably in the form of insoluble particles, but not in the giraffe hair; Mg, Ca, Sr, Ba, and Mn are enhanced on the elephant hair surface by exogenous contaminations, but a comparable amount was found in the hair interior suggesting migration of these elements from the surface towards the core; Cu, Zn, Se, and Pb did not have surface accumulation and thus were dominated by the endogenous signal. Overall, giraffe hair had minimal surficial contamination, suggesting the origin of its trace elements is predominantly endogenous, except for Mn, which might get contaminated with airborne particles. We thus demonstrate that contamination of hair may be strongly related to behavioral traits and that the interpretation of trace elemental analyses in hair as a biomonitor or for provenance studies would be highly dependent on the species considered.

Evidence of upgrading of gold tenor in an orogenic quartz-carbonate vein system by late magmatic-hydrothermal fluids at the Madrid Deposit, Hope Bay Greenstone Belt, Nunavut, Canada

Evidence of secondary gold enrichment due to the addition of new gold into an earlier orogenic quartz-carbonate vein deposit by magmatic-hydrothermal fluids is strongly suggested for the Madrid Deposit, hosted in the Hope Bay Greenstone Belt in Nunavut, Canada. The conclusion is based on an extensive in situ microanalytical protocol (SEM, confocal Raman microspectroscopy, microthermometry, decrepitate mound analysis, LA-ICP-MS, cathodoluminescence, SIMS) not previously applied to gold systems. This approach was used to characterize the mineralogy and fluid inclusion systematics associated with the upgrading event.Mineralization comprised of only Ag-bearing gold (“electrum”; 89.8 at. % Au avg.; n = 8) is present throughout all investigated laminated and brecciated orogenic quartz veins. However, in high-grade vein intersections where gold grades are locally elevated (up to 122 g/t), assemblages containing tennantite-tetrahedrite + chalcopyrite + electrum (80.7 at. % Au avg.; n = 15) ± AgPbAu tellurides occur that are texturally late-stage relative to electrum-only mineralization. Subdomains of quartz coeval with this later assemblage are optically- and texturally-distinct from earlier orogenic quartz. This late mineral assemblage is absent in all low-grade vein intersections (∼1 g/t Au avg.) examined where only electrum is identified. Quartz-hosted fluid inclusions (H2ONaCl ± CO2) of intermediate salinity (16.7 ± 1.2 wt.% NaCl equiv.; n = 93) were identified only in the high-grade vein samples and are present along healed planes associated with tennantite-tetrahedrite + chalcopyrite + electrum ± AgPbAu telluride assemblages. In situ SIMS δ18O analyses of quartz, combined with temperature constraints from mineral equilibria, show that early orogenic vein quartz and late quartz subdomains associated with gold upgrading precipitated from fluids with similar δ18OH2O values of 4.5–12.4‰ (n = 10) and −5.5 to 11.8‰ (n = 13), respectively. Isotopic data suggests that meteoric water was a negligible component in fluids responsible for gold precipitation. Microthermometry and Raman spectroscopy show that upgrading fluids were distinct in composition compared to the earlier metamorphic fluids (H2ONaClCO2 ± CH4 ± N2; 4.6 ± 1.6 wt.% NaCl equiv., n = 33) and later Canadian Shield basement brines (H2ONaCl; 22.4 ± 1.2 wt.% NaCl equiv., n = 12) which have also been identified in the fluid inclusion record at Madrid. Laser ablation ICP-MS analyses indicate the gold upgrading fluids are enriched in AsSbZnPb and LILE (CsBaRbSr); these data are consistent with late fluids derived from an evolved magmatic-hydrothermal system. Trace element mapping of pyrite, coupled with principle component analysis of the data, confirms a strong correlation between Au and AgTeSbBiW(As) in upgraded veins, whereas only Au and As strongly correlate in low-grade veins.The study suggests that gold upgrading, either involving newly introduced gold or remobilization of existing gold, can be linked to the incursion of a late magmatic-hydrothermal fluid that post-dated formation of the main orogenic-type auriferous quartz vein system. The geological setting and mineral-chemical features suggest an intrusion-related (i.e., porphyry), or intermediate-sulfidation epithermal mineralization style for the later event. This work provides another example of the importance of compositionally distinct cumulative hydrothermal events in the development of high-grade gold deposits in orogenic settings.

Fenitization in the giant Bayan Obo REE-Nb-Fe deposit: Implication for REE mineralization

Fenitization, a unique type of alkali metasomatism related to carbonatite or alkaline igneous rocks, is widely distributed around the Mesoproterozoic carbonatite dykes in the Bayan Obo giant REE-Nb-Fe deposit. Meanwhile, represented by alkali silicates (sodic amphibole or aegirine) enriched REE-(Fe) ores, there is extensive alkali alteration in ores at Bayan Obo, whose similarity to fenitization has been proposed. Fenitization associated with carbonatite is an appropriate indicator of REE mineralizing process. Alkali silicates (sodic amphibole, aegirine and phlogopite) from the East and Main open pits, and fenite around the Wu dyke at Bayan Obo were collected for EMPA and laser ablation ICPMS analyses. Aegirine and phlogopite from the open pits and fenite around the Wu dyke contain similar major components. Sodic amphiboles from those two localities contain comparable trace element composition but with different Cao, MgO and F contents. Alkali silicates from fenites around the Wu dyke show systematic enrichment of Zr, Hf and Ti over alkali silicates from the open pits. Considering different wallrocks and other factors influencing the composition, combined with previous results of geochronology, mineralogy and fluid inclusion, the alkali alteration in the open pits is essentially fenitization in ore-hosting dolomite. A two-stage fenitization process is supported by the zonal texture of sodic amphiboles from Wu carbonatite dyke. The early stage fenitization was Mg, Na, K, F rich and Fe, La, Ce depleted, distributed in alkali silicates from the banded REE-Fe ores and in the core of sodic amphiboles from the Wu dyke. The late stage was Fe, LREE rich and Mg, Na, K, F depleted, distributed in the massive REE-(Fe) ores and the rim of sodic amphiboles from the Wu dyke. The initial alkali fluids derived from carbonatite commonly exhibits LREE-rich patterns. Therefore, the LREE-depletion and low La/Nd ratio of the early stage silicates indicates intense LREE-bearing mineral precipitation and the REE mineralization gradually weakened in the late stage when alkali fluids kept the initial REE patterns unchanged.

Subsurface deposition of Cu-rich massive sulphide underneath a Palaeoproterozoic seafloor hydrothermal system—the Red Bore prospect, Western Australia

The Proterozoic Bryah and Yerrida basins of Western Australia contain important base and precious metal deposits. Here we present microtextural data, trace element and S isotope analyses of massive sulphide mineralisation hosted in Palaeoproterozoic subvolcanic rocks (dolerite) recently discovered at Red Bore. The small-scale high-grade mineralisation, which extends from the sub-surface to at least 95 m down-hole, is dominated by massive chalcopyrite and contains minor pyrite and Bi-Te-(Se) phases. Massive sulphide mineralisation is surrounded by discontinuous brecciated massive magnetite, and a narrow (< 2 m) alteration halo, which suggests very focussed fluid flow. Laser ablation ICP-MS analyses indicate that chalcopyrite contains up to 10 ppm Au and in excess of 100 ppm Ag. Sulphur isotope analyses of pyrite and chalcopyrite indicate a narrow range of δ34SVCD (− 0.2 to + 4.6 ‰), and no significant mass-independent fractionation (− 0.1 < Δ33S < + 0.05 ‰). Re-Os isotope analyses yield scattered values, which suggests secondary remobilisation. Despite the geographical proximity and the common Cu-Au-Ag association, the mineralisation at Red Bore has significant differences with massive sulphide mineralisation at neighbouring DeGrussa, as well as other massive sulphide deposits around the world. These differences include the geometry, sub-volcanic host rocks, extreme Cu enrichment and narrow δ34S ranges. Although a possible explanation for some of these characteristics is leaching of S and metals from the surrounding volcanic rocks, we favour formation as a result of the release of a magmatic fluid phase along very focussed pathways, and we propose that mixing of this fluid with circulating sea water contributed to sea floor mineralisation similar to neighbouring VHMS deposits. Our data are permissive of a genetic association of Red Bore mineralisation with VHMS deposits nearby, thus suggesting a direct connection between magmatism and mineralising fluids responsible for VHMS deposition at surface. Therefore, the Red Bore mineralisation may represent the magmatic roots of a VHMS system.

A new method to deconvolute binary mixture in LA-ICP-MS analyses to quantify the composition of phases smaller than the laser spot size

New quantification strategy to deconvolute the data signal of a binary mixture in laser ablation ICP-MS analysis.

The distribution of fluid mobile and other incompatible trace elements in orthopyroxene from mantle wedge peridotites

Orthopyroxene is especially suited to decode and testify to the behavior of highly immobile elements during hydrous mantle melting. Laser ablation ICP-MS analyses from orthopyroxene hosted within peridotite from the Coast Range ophiolite (CRO) demonstrates that Group A peridotites (lherzolites) have similar compositions to mid-ocean-ridge abyssal peridotite, whereas other peridotites (Groups B and C; harzburgites) retain depleted signatures, but display ‘spoon-shaped’ enrichments for the light-REE. These patterns are consistent with variable degrees of partial melting of MORB-source asthenosphere initiated within the garnet stability field (<10%) and continuing into the spinel stability field (<15%). A few samples may have been subjected to subsequent melt/rock interaction. The supra-subduction zone (SSZ) environment represented by the CRO is illustrated by enriched fluid mobile elements (Li, Be, B, Pb) in all samples - up to 200× depleted-MORB mantle (DMM). New applications of trace-element addition calculations [Shervais J. and Jean M.M. (2012) Inside the subduction factory: Modeling fluid mobile element enrichment in the mantle wedge above a subduction zone. GCA 95, 270–285] modified for orthopyroxene reveals that tens to hundreds of ppm were added to the DMM-source region. Our purpose is to demonstrate that orthopyroxene, in the absence of clinopyroxene, can be a constructive (and perhaps better) indicator of tectonic environment and magmatic processes that occurred within the North American Cordillera mantle wedge. Through this investigation we have captured all three stages of Coast Range ophiolite petrogenesis: starting with initial SSZ-coupled forearc spreading dominated by decompression melting, to a mature subduction zone with fluid-assisted partial melting, and the transition between the two.

Texture and chemistry of pyrite at Chah Zard epithermal gold–silver deposit, Iran

Gold mineralization at Chah Zard, Iran, is mostly concentrated in breccia and veins, and is closely associated with pyrite. Optical and scanning electron microscopy-backscattered electron observations indicate four different pyrite types, each characterized by different textures: porous and fractured py1, simple-zoned, oscillatory-rimmed, framboidal and fibrous py2, colloform py3, and inclusion-rich py4. Laser ablation ICP–MS analysis and elemental mapping reveal the presence of invisible gold in all pyrite types. The highest concentrations (161–166ppm Au) are found in py2 and py4, which correlate with the highest As concentrations (73,000–76,000ppm). In As-poor grains, Au concentrations decrease by about two orders of magnitude. Copper, Pb, Zn, Te, Sb, and Ag occur with invisible gold, suggesting that at least part of the gold occurs in nanoparticles of sulfosalts of these metals and metalloids. Gold distribution patterns suggest that only negligible Au was originally trapped in py1 from the initial ore fluids. However, most, if not all, Au was transported and deposited during subsequent overprinting hydrothermal fluid flow in overgrowth rims around the margins of the py2 and within microfractures of py4 grains. Oscillatory zonation patterns for Co, Ni, Sb, Cu, Pb, and Ag in pyrite reflect fluctuations in the hydrothermal fluid chemistry. The LA-ICP–MS data reveal that Cu, Pb and Ag show systematic variations between different pyrite types. Thus, Cu/Pb and Pb/Ag ratios in pyrite may provide a potentially powerful exploration vector to epithermal gold mineralization at Chah Zard district and elsewhere.

The effect of Mg and Sr on the crystallinity of bones evaluated through Raman spectroscopy and laser ablation-ICPMS analysis.

We investigated the possible linkage between the crystallinity and elemental ratios (Mg/Ca and Sr/Ca) of the femoral cortical bones of rats with chronic kidney disease (CKD) or diabetes mellitus (DM). The Mg/Ca and Sr/Ca ratios were measured by using the laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) technique and the crystallinity was evaluated by Raman spectroscopy on the same sample slice. The measured crystallinity varied significantly along the radial direction, reflecting the heterogeneities in the Mg/Ca ratio for the bone samples. For the endosteal cortical bone of CKD rats, the Mg/Ca ratio became higher. This is explained by the increase of the abundance of Mg in the bone, possibly due to the higher absorption efficiency of Mg in the intestine or due to the lower excretion efficiency of Mg from the kidney. For areas with a higher Mg/Ca ratio, the crystallinity of the bone was significantly more degraded than that for areas with a lower Mg/Ca ratio, suggesting that the substitution of Ca by Mg induced the deterioration of the crystallinity of hydroxyapatite (HAp). In addition, the measured Mg/Ca and Sr/Ca ratios of the bone were positively correlated with those found in serum samples. The data obtained here demonstrated that the metabolic alterations for inorganic elements caused the ionic substitutions of Ca by foreign cationic ions, and that the contents of foreign ions in the bone greatly affected the crystallinity of HAp.

U–Pb and Re–Os Geochronology of the Hucunnan Copper–Molybdenum Deposit in Anhui Province, Southeast China, and its Geological Implications

AbstractThe Middle–Lower Yangtze Region (MLYR) is one of the most important metallogenic belts in China that hosts numerous Cu–Fe–Au–S deposits. The Hucunnan deposit in the central part of MLYR is a newly discovered porphyry–skarn‐type copper–molybdenum deposit during recent drilling exploration. Laser ablation ICP–MS analysis carried out in this study yields U–Pb isotopic ages of 137.5 ± 1.2 Ma for the Cu–Mo bearing granodiorite rock and 125.0 ± 1.5 Ma for the Cu‐bearing quartz diorites. The Re–Os isotopic dating of seven molybdenite samples gave an isochron age of 139.5 ± 1.1 Ma, suggesting a syn‐magma mineralization of molybdenite in the Hucunnan deposit. Since porphyry‐type molybdenum deposits are rare in central MLYR, the discovery of the Hucunnan deposit suggests possible molybdenite mineralizations in the deep places of the Cu–Mo bearing granitoids. In addition, the U–Pb isotopic age of 125 Ma for the Cu‐bearing quartz diorites implies a new Cu mineralization period for the MLYR that was rarely reported by previous studies.

Alkali element background reduction in laser ICP-MS

Abstract. Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionisation of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high-alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary, both can easily be applied to the routine operations of an analytical lab.

The role of evaporites in the formation of magnetite–apatite deposits along the Middle and Lower Yangtze River, China: Evidence from LA-ICP-MS analysis of fluid inclusions

Numerous magnetite–apatite deposits occur in the Ningwu and Luzong sedimentary basins along the Middle and Lower Yangtze River, China. These deposits are located in the contact zone of (gabbro)-dioritic porphyries with surrounding volcanic or sedimentary rocks and are characterized by massive, vein and disseminated magnetite–apatite±anhydrite mineralization associated with voluminous sodic–calcic alteration. Petrologic and microthermometric studies on multiphase inclusions in pre- to syn-mineralization pyroxene and garnet from the deposits at Meishan (Ningwu basin), Luohe and Nihe (both in Luzong basin) demonstrate that they represent extremely saline brines (~90wt.% NaClequiv) that were trapped at temperatures of about 780°C. Laser ablation ICP-MS analyses and Raman spectroscopic studies on the natural fluid inclusions and synthetic fluid inclusions manufactured at similar P–T conditions reveal that the brines are composed mainly of Na (13–24wt.%), K (7–11wt.%), Ca (~7wt.%), Fe (~2wt.%), Cl (19–47wt.%) and variable amounts of SO4 (3–39wt.%). Their Cl/Br, Na/K and Na/B ratios are markedly different from those of seawater evaporation brines and lie between those of magmatic fluids and sedimentary halite, suggesting a significant contribution from halite-bearing evaporites. High S/B and Ca/Na ratios in the fluid inclusions and heavy sulfur isotopic signatures of syn- to post-mineralization anhydrite (δ34SAnh=+15.2 to +16.9‰) and pyrite (δ34SPy=+4.6‰ to +12.1‰) further suggest a significant contribution from sedimentary anhydrite. These interpretations are in line with the presence of evaporite sequences in the lower parts of the sedimentary basins.The combined evidence thus suggests that the magnetite–apatite deposits along the Middle and Lower Yangtze River formed by fluids that exsolved from magmas that assimilated substantial amounts of Triassic evaporites during their ascent. Due to their Fe-oxide dominated mineralogy, their association with large-scale sodic–calcic alteration and their spatial and temporal associations with subvolcanic intrusions we interpret them as a special type of IOCG deposits that is characterized by unusually high contents of Na, Ca, Cl and SO4 in the ore-forming fluids. Evaporite assimilation apparently led to the production of large amounts of high-salinity brine and thus to an enhanced capacity to extract iron from the (gabbro)-dioritic intrusions and to concentrate it in the form of ore bodies. Hence, we believe that evaporite-bearing sedimentary basins are more prospective for magnetite–apatite deposits than evaporite-free basins.

Differential effects of cleaning procedures on the trace element chemistry of planktonic foraminifera

We have investigated the effects of different sample cleaning procedures on six trace element/Ca ratios in Globigerina bulloides, a planktonic species widely used in palaeoenvironmental reconstructions. Foraminifera from core-top and down-core sediments were cleaned using seven different methods. Individual foraminifera were analysed before and after cleaning using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). We present a comparison between oxidative and reductive cleaning, and an analysis of the effect of using laser ablation versus solution-based ICPMS methods. Measurements of Mg/Ca and Sr/Ca values were identical whether samples were subjected to oxidative, reductive treatments, two-four acid leach treatments or a combination thereof. However, ultra trace element ratios Al/Ca, Mn/Ca, Zn/Ca and Ba/Ca are much more sensitive to the cleaning method, with up to an order of magnitude difference between techniques. Al/Ca was progressively removed with more intensive cleaning, but six or more acid leach treatments were required for full removal of this contaminant phase. Mn/Ca and Ba/Ca required a combination of oxidative and reductive and/or acid leaching for contaminant phase removal. By contrast, Zn/Ca values increased after acid leaching cleaning procedures. This may be a reflection of preferential dissolution of low-Zn calcite. Accurate measurement of Zn/Ca in planktonic foraminifera by solution methods requires oxidative and reductive treatment without acid leaching or alternatively, the use of an in situ method such as laser ablation ICPMS. Careful data processing following laser ablation ICPMS analysis appears to be the most effective method to ensure elimination of ultra trace metal TE/Ca contaminant phases.

Laser ablation ICP-MS analysis of individual glass shards from tephra deposits – recent developments in trace element micro-analysis and Pb isotope determination

Laser ablation ICP-MS analysis of individual glass shards from tephra deposits – recent developments in trace element micro-analysis and Pb isotope determination

Pyrite trace element geochemistry of mafic granulite xenoliths from Xikeer: implications for the source of Cu in the sediment-hosted mineralization in the northwestern Tarim Basin (Northwest China)

The Xikeer mafic granulite xenoliths are hosted by a Cenozoic basanite sill (∼20 Ma) in the northwest Tarim Basin, northwest China. Sulfides, identified in these xenoliths consist mainly of pyrite. Two groups of pyrite (types A and B) can be distinguished based on petrography and trace element geochemistry, as determined by laser-ablation ICP-MS analysis. Type A pyrite is subhedral and in general has lower trace element abundance than type B pyrite. Type B pyrite is fractured with ragged anhedral morphology and has extremely high Cu, Tl, Ni, and Co abundance. The low Co and Ni contents combined with a positive correlation between Cu, Cr, and Pb all indicate that the type A pyrite may have formed from a high-temperature magmatic hydrothermal fluid. In contrast, the Cu-, Tl-, Ni-, and Co-rich type B pyrite was probably formed in a relatively low-temperature basinal environment. The Cu mineralization at Xikeer can be explained when Cu, Tl, Ni, and Co were leached from the intruded basanites and subsequently enriched in circulating basin brines. Such enrichment of Cu in basin brines could provide an important Cu source for the Cu mineralization in the Xikeer district and other Cenozoic sub-basins in the Tarim Basin.

Post-collisional polycyclic plutonism from the Zagros hinterland: the Shaivar Dagh plutonic complex, Alborz belt, Iran

AbstractThe petrological and geochronological study of the Cenozoic Shaivar Dagh composite intrusion in the Alborz Mountain belt (NW Iran) reveals important clues to decipher complex relations between magmatic and tectonic processes in the central sectors of the Tethyan (Alpine–Himalayan) orogenic belt. This pluton is formed by intrusion at different times of two main magmatic cycles. The older (Cycle 1) is formed by calc-alkaline silicic rocks, which range in composition from diorites to granodiorites and biotite granites, with abundant mafic microgranular enclaves. The younger cycle (Cycle 2) is formed by K-rich monzodiorite and monzonite of marked shoshonitic affinity. The latter form the larger volumes of the exposed plutonic rocks in the studied complex. Zircon geochronology (laser ablation ICP-MS analyses) gives a concordia age of 30.8 ± 2.1 Ma for the calc-alkaline rocks (Cycle 1) and a range from 23.3 ± 0.5 to 25.1 ± 0.9 Ma for the shoshonitic association (Cycle 2). Major and trace element relations strongly support distinct origins for each magmatic cycle. Rocks of Cycle 1 have all the characteristic features of active continental margins. Shoshonitic rocks (Cycle 2) define two continuous fractionation trends: one departing from a K-rich basaltic composition and the other from an intermediate, K-rich composition. A metasomatized-mantle origin for the two shoshonitic series of Cycle 2 is proposed on the basis of comparisons with experimental data. The origin of the calc-alkaline series is more controversial but it can be attributed to processes in the suprasubduction mantle wedge related to the incorporation of subducted mélanges in the form of silicic cold plumes. A time sequence can be established for the processes responsible of the generation of the two magmatic cycles: first a calc-alkaline cycle typical of active continental margins, and second a K-rich cycle formed by monzonites and monzodiorites. This sequence precludes the younger potassic magmas as precursors of the older calc-alkaline series. By contrast, the older calc-alkaline magmas may represent the metasomatic agents that modified the mantle wedge during the last stages of subduction and cooked a fertile mantle region for late potassic magmatism after continental collision.

Contrasting matrix induced elemental fractionation in NIST SRM and rock glasses during laser ablation ICP-MS analysis at high spatial resolution

The greatest strength of the LA-ICP-MS technique is its application to microsampling in which extremely small pits are obtained. The results of this study highlight some significant different laser-induced fractionations between widely used external reference materials NIST SRM 610–614 and natural silicate reference materials (e.g., USGS reference glasses (GSE-1G, GSD-1G), MPI-DING glasses, USGS basalt glasses and zircon reference material GJ-1) at high spatial resolution analysis. For the sample matrices and analytical conditions used in this study, the laser-induced elemental fractionations for 63 selected isotopes are negligible at the spot sizes of 160–44 µm. However, the laser-induced elemental fractionations of Li, Na, Si, K, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Cs and U (with respect to Ca) increase significantly with decreasing spot sizes from 44 µm to 32 µm, 24 µm and 16 µm in these natural silicate reference materials. Unlike in these sample matrices, laser-induced elemental fractionations of these elements in NIST SRM 610–614 are unique in that they are almost not affected by the change of spot sizes from 44 to 32 to 24 µm, with only slight increase at the spot sizes of 16 µm. The much less significant laser-induced elemental fractionation in NIST SRM 61X in comparison with other natural silicate materials makes them not ideal as external reference materials at high spatial resolution analysis. Alternatively, this NIST SRM 61X-specific matrix effect for Li, Na, K, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Cs and U can be minimized by using Si for internal standardization. U and Pb in zircon GJ-1 are exceptions, which are zircon-specific.

A new approach for calibration of laser ablation inductively coupled plasma mass spectrometry using thin layers of spiked agarose gels as references

Calibration of analytical methods using laser ablation for sample introduction is often problematic. The availability of matrix-adapted standard materials is a crucial factor in the analysis of biological samples in particular. In this work a method for preparation of thin-film references for LA-ICP-MS is presented which is inexpensive, relatively simple and generally practicable. Aqueous solutions of agarose spiked with defined amounts of the analytes were cast on a carrier and then dried. When the thin-film references were characterized the average thickness of the films was 0.03 mm in the centre of the film and the relative standard deviation was 8%. Nebulization ICP-MS analysis after acid digestion of the agarose film was used to investigate the effectiveness of the spiking procedure. Recovery of the spiked elements was frequently in the range 90-110% (for rare earth elements 97-102%). Laser ablation ICP-MS analysis was used to investigate the distribution of the spiked elements in the film. When the laser was scanned across the gel the measured intensities were not constant, but had a peak-shaped profile with a flat top. Use of this flat-top region for analytical purposes, after its characterization by laser ablation ICP-MS, is proposed. Analysis of cell cultures was carried out by direct laser ablation-ICP-MS with the calibration method described. The results were in accordance with values previously achieved by nebulization ICP-MS.

The challenge of direct dating old human fossils

This paper reviews the possible approaches for dating of human bones and teeth, older than 500,000 years. Skeletal tissues can, in principle, be dated with an open-system U-series approach, which requires that the Th/U activity ratio is still below equilibrium. This indicates that the sample experienced continuing U-uptake. To gain insights about the state of U-series isotopes in old samples, laser ablation ICP-MS analysis was used for the detailed mapping of U-series isotopes in a 1.2 Ma old horse tooth from the archaeological site of Fuente Nueva III (Orce, Andalusia, Spain). The maps show a complex system of U-migration in and out of the dental tissues. There are clearly domains in the dentine of the tooth where the Th/U ratios indicate continuing U-accumulation. These domains could be extracted and used for open-system U-series dating Firstly, the diffusion–adsorption model could be applied for open-system U-series dating of bones well beyond one million years. The practical difficulty of this approach is whether there are actually any old samples that conform to the D-A model. The horse tooth from Fuente Nueva III, for example, was definitely not suitable for D-A dating. Secondly, a combination of Th/U–Pa/U dating could be applied on bones. When calculating open-system Th/U–Pa/U isotope evolution diagrams with isochrons, it turns out that dating is theoretically possible to perhaps one million years. However, even the presently most precise analytical results would be associated with errors that will prevent dating beyond about 600–700 ka, because the isochrons beyond this time range become very tightly spaced. Lastly, a combination of ESR and U-series analyses can be used in ideal circumstances for dating teeth up to several millions of years of age.